EP0082211B2 - Mit Silicium substituierte Zeolithzusammensetzungen und Verfahren zu ihrer Herstellung - Google Patents

Mit Silicium substituierte Zeolithzusammensetzungen und Verfahren zu ihrer Herstellung Download PDF

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EP0082211B2
EP0082211B2 EP19810110629 EP81110629A EP0082211B2 EP 0082211 B2 EP0082211 B2 EP 0082211B2 EP 19810110629 EP19810110629 EP 19810110629 EP 81110629 A EP81110629 A EP 81110629A EP 0082211 B2 EP0082211 B2 EP 0082211B2
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zeolite
starting
zeolitic aluminosilicate
framework
silicon
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EP0082211A1 (de
EP0082211B1 (de
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Gary William Skeels
Donald Wesley Breck
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Union Carbide Corp
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Union Carbide Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/026—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
    • C07C5/2708—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously with crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof

Definitions

  • the crystal structures of naturally occurring and as-synthesized zeolitic aluminosilicates are composed of A104 and Si0 4 tetrahedra which are cross-linked by the sharing of oxygen atoms.
  • the electrovalence of each tetrahedron containing an aluminum atom is balanced by association with a cation.
  • this cation is a metal cation such as Na + or K + but organic species such as quaternary ammonium ions are also employed in zeolite synthesis and in some instances appear as cations in the synthesized product zeolite.
  • the metal cations are, to a considerable extent at least, replaceable with other cations including H + and NH 4 + .
  • the organic cation species are too large to pass through the pore system of the zeolite and hence cannot be directly replaced by ion exchange techniques.
  • Thermal treatments can reduce these organic cations to H + or NH 4 + cations which can be directly ion-exchanged.
  • Thermal treatment of the H + or NH 4 + cationic forms of the zeolites can result in the substantial removal of these cations from their normal association with the AlO 4 - tetrahedra thereby creating an electrovalent imbalance in the zeolite structure which must be accompanied by structural rearrangements to restore the eletrovalent balance.
  • infrared analysis indicated the presence of substantial hydroxyl groups exhibiting a stretching frequency in the area of about 3740, 3640 and 3550 cm- 1 .
  • the infrared analytical data of US-Patent 3,506,400 is especially instructive in this regard. An explanation of the mechanism of the creation of these hydroxyl groups is provided by Kerr et al.
  • US-Patent 4,273,753 discloses the treatment of an alumino-silicate-zeolite with SiC1 4 at temperatures of above 140°C. It is assumed that not only aluminum is removed from the zeolite framework but also silicon atoms are incorporated in the vacancies that are formed as a result of the de-alumination. This assumption is purely speculative and not evidenced by any facts.
  • a fluoride treatment of this type using from 2 to 22 grams of available fluoride per 10,000 grams of zeolite (anhydrous) in which the fluorine is provided by ammonium fluorosilicate is also described therein.
  • the treatment is carried out for the purpose of improving the thermal stability of the zeolite. It is theorized by the patentee that the fluoride in some manner becomes attached to the constructional alkali metal oxide, thereby reducing the fluxing action of the basic structural Na 2 0 which would otherwise result in the collapse of the crystal structure.
  • Such treatment within the constraints of the patent disclosure has no effect on either the overall silicon content of the zeolite product or the silicon content of a unit cell of the zeolite.
  • the process comprises contacting a crystalline zeolite having pore diameters of at least about 3.10- 4 ⁇ m and having a molar Si0 2 /AI 2 0 3 ratio of at least 3, with a fluorosilicate salt, preferably in an amount of at least 0.0075 moles per 100 grams of zeolite starting material, said fluorosilicate salt being in the form of an aqueous solution having a pH value in the range of 3 to about 7, preferably 5 to about 7, and brought into contact with the zeolite either incrementally or continuously at a slow rate whereby framework aluminum atoms of the zeolite are removed and replaced by extraneous silicon atoms from the added fluorosilicate.
  • the process is carried out such that at least 60, preferably at least 80, and most preferably at least 90, percent of the crystal structure of the starting zeolite is retained and the Defect Structure Factor is less than 0.08, and preferably less than 0.05 as defined hereinafter.
  • the crystalline zeolite starting materials suitable for the practice of the present invention can be any of the well known naturally occurring or synthetically produced zeolite species which have pores large enough to permit the passage of water, fluorosilicate reagents and reaction products through their internal cavity system. These materials can be represented, in terms of molar ratios of oxides, as wherein "M” is a cation having the valence "n”, “x” is a value of at least about 3 and "y” has a value of from zero to about 9 depending upon the degree of hydration and the capacity of the particular zeolite to hold adsorbed water.
  • the framework composition can be expressed as the mole fraction of framework tetrahedra, T0 2 , as: wherein "a” is the fraction of framework tetrahedral sites occupied by aluminum atoms and "b” is the fraction of framework tetrahedral sites occupied by silicon atoms.
  • T0 2 mole fraction of framework tetrahedra
  • the starting zeolite be able to withstand the initial loss of framework aluminum atoms to at least a modest degree without collapse of the crystal structure unless the process is to be carried out at a very slow pace.
  • the ability to withstand aluminum extraction and maintain a high level of crystallinity is directly proportional to the initial Si0 2 /AI 2 0 3 molar ratio of the zeolite. Accordingly it is preferred that the value for "x" in the formula above be at least about 3, and more preferably at least about 3.5.
  • the starting zeolite contains as many as possible of its original A10 4 tetrahedra, i.e. has not been subjected to any post-formation treatment which either extensively removes aluminum atoms from their original framework sites or converts them from the normal conditions of 4-fold coordination with oxygen.
  • the cation population of the starting zeolite is not a critical factor insofar as substitution of silicon for framework aluminum is concerned, but since the substitution mechanism involves the in situ formation of salts of at least some of the zeolitic cations, it is advantageous that these salts be water-soluble to a substantial degree to facilitate their removal from the silica-enriched zeolite product. It is found that ammonium cations form the most soluble salt in this regard and it is accordingly preferred that at least 50 percent, most preferably 85 or more percent, of the zeolite cations be ammonium cations.
  • the naturally-occurring or synthetic zeolites used as starting materials in the present process are compositions well-known in the art. A comprehensive review of the structure, properties and chemical compositions of crystalline zeolites is contained in Breck, D. W. "Zeolite Molecular Sieves", Wiley, New York, 1974. In those instances in which it is desirable to replace original zeolitic cations for others more preferred in the present process, conventional ion-exchange techniques are suitably employed.
  • zeolite Y zeolite Y
  • zeolite rho zeolite W
  • zeolite N-A zeolite L
  • the mineral and synthetic analogs of mordenite clinoptilolite chabazite, offretite and erionite.
  • the fluorosilicate salt used as the aluminum extractant and also as the source of extraneous silicon which is inserted into the zeolite structure in place of the extracted aluminum can be any of the fluorosilicate salts having the general formula wherein A is a metallic or non-metallic cation other than H + having the valence "b".
  • Cations represented by "A” are alkylammonium, NH 4 + , Mg ++ , Li + , Na + , K + , Ba ++ , Cd ++ , Cu + , H + , Ca ++ , Cs + , Fe ++ , Co ++ , Pb ++ , Mn ++ , Rb + , Ag + , Sr ++ , TI + and Zn ++ .
  • the ammonium cation form of the fluorosilicate is highly preferred because of its substantial solubility in water and also because the ammonium cations form water soluble by-product salts upon reaction with the zeolite, namely (NH 4 ) 3 AIF 6 .
  • the manner in which the fluorosilicate and starting zeolite are brought into contact and reacted is of critical importance.
  • the overall process of substituting silicon for aluminum in the zeolite framework is a two step process in which the aluminum extraction step will, unless controlled, proceed very rapidly while the silicon insertion is relatively very slow. If dealumination becomes too extensive without silicon substitution, the crystal structure becomes seriously degraded and ultimately collapses.
  • the fluoride ion is the agent for the extraction of framework aluminum in accordance with the equation. It is, therefore, essential that the initial dealumination step be inhibited and the silicon insertion step be promoted to achieve the desired zeolite product.
  • the various zeolite species have varying degrees of resistance toward degradation as a consequence of framework aluminum extraction without silicon substitution.
  • rate of aluminum extraction is decreased as the pH of the fluorosilicate solution in contact with the zeolite is increased within the range of 3 to 7, and as the concentration of the fluorosilicate in the reaction system is decreased.
  • concentration of the fluorosilicate in the reaction system is decreased.
  • increasing the reaction temperature tends to increase the rate of silicon substitution. Whether it is necessary or desirable to buffer the reaction system or strictly limit the fluorosilicate concentration is readily determined for each zeolite species by routine observation.
  • the preferred reaction temperature is within the range of 50 to 95°C., but temperatures as high as 125°C and as low as 20°C have been suitably employed in some instances. At pH values below about 3 crystal degradation is generally found to be unduly severe, whereas at pH values higher than 7, silicon insertion is unduly low.
  • the maximum concentration of fluorosilicate salt in the aqueous solution employed is, of course, interdependent with the temperature and pH factors and also with the time of contact between the zeolite and the solution and the relative proportions of zeolite and fluorosilicate.
  • solutions having fluorosilicate concentrations of from about 10- 3 moles per liter of solution up to saturation can be employed, but it is preferred that concentrations in the range of 0.5 to 1.0 moles per liter of solution be used. These concentration values are with respect to true solutions, and are not intended to apply to the total fluorosilicate in slurries of salts in water. As illustrated hereinafter, even very slightly soluble fluorosilicates can be slurried in water and used as a reagent-the undissolved solids being readily available to replace dissolved molecular species consumed in reaction with the zeolite.
  • the amount of dissolved fluorosilicate employed with respect to the particular zeolite being treated will depend to some extent upon the physical and chemical properties of the individual zeolites as well as other specifications herein contained in this application. However, the minimum value for the amount of fluorosilicate to be added should be at least equivalent to the minimum mole fraction of aluminum to be removed from the zeolite.
  • the anhydrous state of the zeolite will be intended unless otherwise stated.
  • the anhydrous state is considered to be that obtained by heating the zeolite in dry air at 450°C for 4 hours.
  • the integrity of the zeolite crystal structure is substantially maintained throughout the process, and that in addition to having extraneous (non-zeolitic) silicon atoms inserted into the lattice, the zeolite retains at least 60 and preferably at least 90 percent of its original crystallinity.
  • Aconvenient technique for assessing the crystallinity of the products relative to the crystallinity of the starting material is the comparison of the relative intensities of the d-spacings of their respective X-ray powder diffraction patterns. The sum of the peak heights, in terms of arbitrary units above background, of the starting material is used as the standard and is compared with the corresponding peak heights of the products.
  • the numerical sum of the peak heights of the product is 85 percent of the value of the sum of the peak heights of the starting zeolite, then 85 percent of the crystallinity has been retained.
  • these d-spacings correspond to the Miller Indices 331,440,533,642 and 555.
  • Other indicia of the crystallinity retained by the zeolite product are the degree of retention of surface area and the degree of retention of the adsorption capacity.
  • this adsorption band or envelope increases with increasing aluminum depletion of the zeolite.
  • the reason that the adsorption band is so broad and without any specific absorption frequency is that the hydroxyl groups in the vacant sites in the framework are coordinated in such a way that they interact with each other (hydrogen bonding).
  • the hydroxyl groups of adsorbed water molecules are also hydrogen-bonded and produce a similar broad absorption band as do the "nest" hydroxyls.
  • certain other zeolitic hydroxyl groups exhibiting specific characteristic absorption frequencies within the range of interest, will if present, cause infrared absorption bands in these regions which are superimposed on the band attributable to the "nest" hydroxyl groups.
  • These specific hydroxyls are created by the decomposition of ammonium cations or organic cations present in the zeolite.
  • the decomposable ammonium cations can be removed, at least in large part, by ion-exchange and replaced with metal cations, preferably by subjecting the ammonium form of the zeolite to a mild ion exchange treatment with an aqueous NaCi solution.
  • the OH absorption bands produced by the thermal decomposition of ammonium cations are thereby avoided. Accordingly the absorption band over the range of 3745 cm- 1 to about 3000 cm- 1 for a zeolite so treated is almost entirely attributable to hydroxyl groups associated with defect structure and the absolute absorbance of this band can be a measure of the degree of aluminum depletion.
  • the absorption frequency least affected by absorption due to hydroxyl groups other than those associated with framework vacancies or defect sites is at 3710 ⁇ 5 cm- 1 .
  • the relative number of defect sites remaining in a zeolite product of this invention can be gauged by first removing any adsorbed water from the zeolite, determining the value of the absolute absorbance in its infrared spectrum at a frequency of 3710 cm- 1 , and comparing that value with the corresponding value obtained from the spectrum of a zeolite having a known quantity of defect structure.
  • the following specific procedure has been arbitrarily selected and used to measure the amount of defect structure in the products prepared in the Examples appearing hereinafter.
  • Standards with known amounts of defect structure can be prepared by treating a crystalline zeolite of the same species as the product sample with ethylenediaminetetraacetic acid by the standard procedure of Kerr as described in US-Patent 3,442,795.
  • the starting zeolite be well crystallized, substantially pure and free from defect structure.
  • the first two of these properties are readily determined by conventional X-ray analysis and the third by infrared analysis using the procedure set forth in part (B) hereof.
  • the product of the aluminum extraction should also be well crystallized and substantially free from impurities.
  • the amount of aluminum depletion, i.e., the mole fraction of tetrahedral defect structure of the standard samples can be ascertained by conventional chemical analytical procedure.
  • the molar Si0 2 /A1 2 0 3 ratio of the starting zeolite used to prepare the standard sample in any given case is not narrowly critical, but is preferably within about 10% of the molar Si0 2 /AI 2 0 3 ratio of the same zeolite species used as the starting material in the practice of the process of the present invention.
  • the infrared spectrum of the wafer is obtained on an interferometer system at 4 cm- 1 resolution over the frequency range of 3745 to 3000 cm- 1 .
  • Both the product sample and the standard sample are analyzed using the same interferometer system to avoid discrepancies in the analysis due to different apparatus.
  • the spectrum, normally obtained in the transmission mode of operation is mathematically converted to and plotted as wave number vs. absorbance.
  • the defect structure factor (z) is calculated by substituting the appropriate data into the following formula: wherein AA (PS) is the infrared absolute absorbance measured above the estimated background of the product sample at 3710 cm- 1 ; AA (std) is the absolute absorbance measured above the background of the standard at 3710 cm- 1 and the mole fraction of defects in the standard are determined in accordance with part (A) above.
  • defect structure factor, z is known, it is possible to determine from wet chemical analysis of the product sample for Si0 2 , A1 2 0 3 and the cation content as M 2Jn O whether silicon has been substituted for aluminum in the zeolite as a result of the treatment and also the efficiency of any such silicon substitution.
  • the framework compositions are best expressed in terms of mole fractions of framework tetrahedra TO 2 .
  • the zeolite product of the fluorosilicate treatment expressed in terms of mole fraction of framework tetrahedra (TO 2 ) will have the form wherein "N" is defined as the mole fraction of aluminum tetrahedra removed from the framework during the treatment; “a” is the mole fraction of the starting zeolite; “b” is the mole fraction of silicon tetrahedra present in the framework of the starting zeolite; “z” is the mole fraction of defect sites in the framework; (N-Az) is the mole fraction increase in silicon tetrahedra resulting from the fluorosilicate treatment; "Az” is the net change in the mole fraction of defect sites in the zeolite framework resulting from the treatment
  • Defect Structure Factor for any given zeolite is equivalent to the "z” value of the zeolite.
  • the net change in Defect Structure Factors between the starting zeolite and the product zeolite is equivalent to "Az". Numericallv. the sum of
  • the essential X-ray powder diffraction patterns appearing in this specification and referred to in the appended claims are obtained using standard X-ray powder diffraction techniques.
  • the radiation source is a high- intensity, copper target, X-ray tube operated at 50 Kv and 40 Ma.
  • the diffraction pattern from the copper K ⁇ radiation and graphite monochromator is suitably recorded by an X-ray spectrometer scintillation counter, pulse-height analyzer and strip-chart recorder.
  • Flat compressed powder samples are scanned at 2° (2 theta) per minute, using a 2 second time constant.
  • Interplanar spacings (d) are obtained from the position of the diffraction peaks expressed as 20, where 0 is the Bragg angle as observed on the strip chart. Intensities are determined from the heights of diffraction peaks after subtracting background.
  • the preferred crystalline aluminosilicate compositions* of the present invention will contain a chemical or molar framework composition which can be determined from the expression of mole fractions of framework tetrahedra previously described; wherein:
  • Crystal structures are more commonly described in terms of the number of tetrahedra in a unit cell.
  • the unit cell is the basic structural unit that is repeated throughout the crystal.
  • the number of tetrahedra in a unit cell vary widely among the various zeolite species, however.
  • the unit cell of offretite contains only 18 tetrahedra whereas the unit cell offaujasite or a Y-type zeolite contains 192 tetrahedra.
  • the substitution of one extraneous silicon atom for one framework aluminum atom in each unit cell of offretite has a disportionately larger effect than the same single atom substitution per unit cell of faujasite.
  • the framework substitutions as changes in the framework density of the zeolites involved, which can be expressed as the number of framework tetrahedra per 10- s wm 3 (10,000 A3). Most zeolites have a framework density of from about 130 to 190 tetrahedra per 10- 8 ⁇ m (10,000 A3).
  • a more detailed description of framework density has been published by W. M. Meier, "Proceedings of the Conference on Molecular Sieve (London, April 1967), "Society of Chemical Industry, (1968) pg. 19 et seq. This publication is incorporated herein by reference. Accordingly, the crystalline aluminosilicates* of the present invention include:
  • Zeolite LZ-210 having, in the dehydrated state, a chemical composition expressed in terms of mole ratios of oxides as wherein "M” is a cation having the valence “n” and “x” is a value greater than 8, preferably greater than 9 more preferably and within the range of 9 to 60, having an X-ray powder diffraction pattern having at least the d-spacings set forth in Table A, below, and having extraneous silicon atoms in its crystal lattice in the form of Si0 4 tetrahedra, preferably in an average amount of at least 1.0 per 10- s ⁇ m 3 (10,000 A3).
  • LZ-210 compositions i.e. those which are characterized by having both high molar Si0 2 /A1 2 0 3 ratios and low Defect Structure Factors, can be defined as having a chemical composition expressed in terms of mole fractions of framework tetrahedra as: wherein:
  • LZ-210 can be prepared from a conventionally prepared zeolite Y which has a molar SiO 2 /Al 2 O 3 ratio of less than 8 by using the present process to increase the Si0 2 /AI 2 0 3 ratio greater than 8.
  • a preferred procedure is the process embodiment which comprises.
  • AFS is the minimum number of moles of ammonium fluorosilicate per 100 gm (anhydrous weight) of zeolite starting material and "a" is the mole fraction of framework aluminum atoms in the zeolite starting material as stated in (Al a Si b ⁇ z )O 2 , said fluorosilicate being in the form of an aqueous solution at a pH in the range of 5 to about 7, the fluorosilicate solution being brought into contact with the zeolite either incrementally or continuously at a slow rate such that a sufficient proportion of the framework aluminum atoms removed are replaced by silicon atoms to retain at least 80 percent, preferably at least 90 percent, of the crystal structure of the starting zeolite Y; and
  • the starting zeolite Y composition can be synthesized by any of the processes well known in the art. Representative processes are disclosed in US-Patent 3,130,007.
  • Another zeolite composition* of the present invention is LZ-211 which has, in the dehydrated state and prior to calcination at a temperature in excess of 200°C a chemical composition expressed in terms of mole ratios of oxides as wherein "M” is an inorganic cation having the valence "n", preferably H + , NH 4 + or a metallic cation, and x is a value greater than 15, preferably within the range of 17 to 120, and most preferably from 17 to 35, having the characteristic crystal structure of mordenite as indicated by an X-ray powder diffraction pattern having at least the d-spacings set forth in Table C, below, and having extraneous silicon atoms in its crystal lattice in the form of Si0 4 tetrahedra, preferably in an average amount of at least 1.0 per 10- 8 wm3 (10,000 A3).
  • M is an inorganic cation having the valence "n”, preferably H + , NH 4 + or a metallic
  • a more limited subclass of LZ-211 compositions i.e. those which are characterized by having both high molar Si0 2 /A1 2 0 3 ratios and low Defect Structure Factors, can be defined as having a chemical composition expressed in terms of mole fractions of framework tetrahedra as: wherein: the mole fraction of aluminum, N, removed from the framework of the starting zeolite is at least 0.3a; the Si/AI ratio has a value 7.5, preferably within the range 8.5 to 30; an increase in the Defect Structure Factor "Az" of less than 0.08, an increase of silicon in the framwork of at least 0.5; a cation equivalent expressed as a monovalent cation species M + /Al of 0.9 ⁇ 0.1.
  • the precursor of LZ-211 i.e. the starting mordenite zeolite
  • the zeolites denominated LZ-214 are the more siliceous forms of the prior known zeolite Rho and are prepared therefrom using the present process for silicon substitution.
  • LZ-214 has, in the dehydrated state, a chemical composition expressed in terms of mole ratios of oxides wherein "M” is a cation having the valence "n” and "x" is a value greater than 7, preferably in the range of 8 * obtained by the method to 60, the characteristic crystal structure of zeolite Rho as indicated by an X-ray powder diffraction pattern having at least the d-spacings set forth in Table D, below and having extraneous silicon atoms in its crystal lattice in the form of Si0 4 tetrahedra, preferably in an amount of at least 1.0 per 10- 8 ⁇ m 3 (10,000 A3).
  • a more limited subclass of LZ-214 compositions i.e. those which are characterized by having both high molar Si0 2 /A1 2 0 3 ratios and low Defect Structure Factors, can be defined as having a chemical composition expressed in terms of mole fraction of framework tetrahedra as: wherein: the mole fraction of aluminum, N, removed from the framework of the starting zeolite Rho is at least 0.3a; the Si/Al has a value ⁇ 4 preferably within the range 4.5 to 30; an increase in the Defect Structure Factor "Az" of less than 0.08, an increase of silicon in the framework, of at least 0,5; a cation equivalent expressed as a monovalent cation species M + /Al of 0.9 ⁇ 0.1.
  • Zeolite Rho and the method for its manufacture are set forth in US-Patent 3,904,738 issued September 9, 1975.
  • the zeolites denominated LZ-212 are the more siliceous forms of the prior known zeolite L and are prepared therefrom using the present process for silicon substitution.
  • LZ-212 has, in the dehydrated state, a chemical composition expressed in terms of mole ratios of oxides wherein "M” is a cation having the valence "n” and "x" is a value greater than 8, preferably in the range of 9 to 60, the characteristic crystal structure of zeolite L as indicated by an X-ray powder diffraction pattern having at least the d-spacings set forth in Table E, below, and having extraneous silicon atoms in its crystal lattice in the form of Si0 4 tetrahedra, preferably in an amount of at least 1.0 per 10- s w m 3 (10,000 A3).
  • a more limited subclass of LZ-212 compositions i.e., those which are characterized by having both high molar Si0 2 /A1 2 0 3 ratios and low Defect Structure Factors, can be defined as having a chemical composition can be expressed in terms of mole fraction of framework tetrahedra as: wherein: the mole fraction of aluminum, N, removed from the framework of the starting zeolite L is at least 0.3a; the Si/Al has a value ⁇ 4; an increase in the Defect Structure Factor, Az, of less than 0.08, an increase of silicon in the framework, of at least 0.5; a cation equivalent expressed as a monovalent cation species M + /Al of 0.9 ⁇ 0.1.
  • Zeolite L and the method for its manufacture are set forth in US-Patent 3,216,789 issued November 9, 1965.
  • the zeolites denominated LZ-215 are the more siliceous forms of the prior known zeolite N-A and are prepared therefrom using the present process forsilicon substitution.
  • LZ-215 has, in the dehydrated state, a chemical composition expressed in terms of mole ratios of oxides wherein "M” is a cation having the valence "n” and "x” is a value greater than 8, preferably in the range of 10 to 30, the characteristic crystal structure of zeolite N-A as indicated by an X-ray powder diffraction pattern having at least the d-spacings set forth in Table F, below, and having extraneous silicon atoms in its crystal lattice in the form of Si0 4 tetrahedra, preferably in an amount of at least 1.0 per 10- s ⁇ m 3 (10,000 A3).
  • a more limited subclass of LZ-215 compositions i.e. those which are characterized by having both high molar Si0 2 /A1 2 0 3 ratios and low Defect Structure Factors, can be defined as having a chemical composition can be expressed in terms of mole fractions of framework tetrahedra as: wherein: the mole fraction of aluminum N, removed from the framework of the starting zeolite N-A is at least 0.3a; the Si/Al has a value ⁇ 4, preferably within the range 5 to 30; an increase in the Defect Structure Factor "Az" of less than 0.08, an increase of silicon in the framework of at least 0.5; a cation equivalent expressed as a monovalent cation species M + /Al of 0.9 ⁇ 0.1.
  • Zeolite N-A and the method for its manufacture are set forth in US-Patent 3,306,922 issued February 23, 1967.
  • the zeolites denominated LZ-216 are the more siliceous forms of the prior known zeolite W and are prepared therefrom using the present process forsilicon substitution.
  • LZ-216 has, in the dehydrated state, a chemical composition expressed in terms of mole ratios of oxides wherein "M” is a cation having the valence "n” and "x" is a value greater than 8, preferably in the range of 8 to 60, the characteristic crystal structure of zeolite W as indicated by an X-ray powder diffraction pattern having at least the d-spacings set forth in Table G, below, and having extraneous silicon atoms in its crystal lattice in the form of Si0 4 tetrahedra, preferably in an amount of at least 1.0 per 10- s ⁇ m 3 (10,000 A3).
  • a more limited subclass of LZ-216 compositions i.e. those which are characterized by having both high molar Si0 2 /A1 2 0 3 ratios and low Defect Structure Factors, can be defined as having a chemical composition expressed in terms of mole fractions of framework tetrahedra as: wherein: the mole fraction of aluminum, N, removed from the framework of the starting zeolite W is at least 0.3a; the Si/Al has a value 4, an increase in the Defect Structure Factor, Az, of less than 0.08, an increase of silicon in the framwork of at least 0.5; a cation equivalent expressed as a monovalent cation species M + /Al of 0.9 ⁇ 0.1.
  • Zeolite W and the method for its manufacture are set forth in US-Patent 3,012,853 issued December 12, 1961.
  • the zeolites denominated LZ-217 are the more siliceous forms of the prior known zeolite mineral offretite and its synthetic analogues, zeolite O and TMA-Offretite, and are prepared therefrom using the present process for silicon substitution.
  • LZ-217 has, in the dehydrated state, a chemical composition expressed in terms of mole ratios of oxides: wherein M is a cation having the valence "n" and "x" has a value of at least 8 and the characteristic crystal structure of offretite as indicated by an X-ray powder diffraction pattern having at least the d-spacings setforth in Table H, below, and having extraneous silicon atoms in its crystal lattice in the form of Si0 4 tetrahedra, preferably in an amount of at least 1.0 per 10 -8 ⁇ m 3 (10,000 A3).
  • a more limited subclass of LZ-217 compositions i.e. those which are characterized by having both high molar Si0 2 /A1 2 0 3 ratios and low Defect Structure Factors, can be defined as having a chemical composition expressed in terms of mole fractions of framework tetrahedra as: wherein: the mole fraction of aluminum, N, removed from the framework of the starting zeolite offretite is at least 0.3a; the Si/Al has a value 4, an increase in the Defect Structure Factor, Az, of less than 0.08, an increase of silicon in the framework, of at least 0.5; a cation equivalent expressed as a monovalent cation species M + /Al of 0.9 ⁇ 0.1.
  • the zeolites denominated LZ-218 are the more siliceous forms of the prior known zeolite mineral chabazite and the structurally related synthetic zeolite R, zeolite G, and zeolite D, and are prepared therefrom using the present process for silicon substitution.
  • LZ-218 has, in the dehydrated state, chemical composition expressed in terms of mole ratios of oxides: wherein M is a cation having the valence "n" and "x" has a value of greater than 8, preferably in the range of 8 to 20, and the characteristic crystal structure of chabazite as indicated by an X-ray powder diffraction pattern having at least the d-spacings set forth in Table I, below, and having extraneous silicon atoms in its crystal lattice in the form of Si0 4 tetrahedra, preferably in an amount of at least 1.0 per 10- 8 ⁇ m 3 (10,000 A3).
  • a more limited subclass of LZ-218 compositions i.e. those which are characterized by having both higher molar Si0 2 /A1 2 0 3 ratios and low Defect Structure Factors, can be defined as having a chemical composition expressed in terms of mole fractions of framework tetrahedra as: wherein: the mole fraction of aluminum, N, removed from the framework of the starting zeolite is at least 0.3a; the Si/Al has a value 4, an increase in the Defect Structure Factor, ⁇ z, of less than 0.08, an increase of silicon in the framework, of at least 0.5, a cation equivalent expressed as a monovalent cation species M + /Al of 0.9 ⁇ 0.1.
  • the zeolites denominated LZ-219 are the more siliceous forms of the prior known zeolite mineral clinoptilolite, and are prepared therefrom using the present process for silicon substitution.
  • LZ-219 has, in the dehydrated state a chemical composition expressed in terms of mole ratios of oxides: wherein M is a cation having the valence "n" and "x" has a value of greater than 11, preferably in the range of 12 to 20, and the characteristic crystal structure of clinoptilolite as indicated by an X-ray powder diffraction pattern having at least the the d-spacings set forth in Table J, below, and having extraneous silicon atoms in its crystal lattice in the form of Si0 4 tetrahedra, preferably in an amount of at least 1.0 per 10- 8 ⁇ m 3 (10,000 A3).
  • a more limited subclass of LZ-219 compositions i.e. those which are characterized by having both higher molar Si0 2 /A1 2 0 3 ratios and low Defect Structure Factors, can be defined as having a chemical composition, expressed in terms of mole fraction of framework tetrahedra as: wherein the mole fraction of aluminum removed, "N", from the starting clinoptilolite is at least 0.3a; a Si/Al ratio of 5.5, preferably greater than 6.0, an increase in the Defect Structure Factor, Az, of less than 0.08; an increase of silicon in the framework, of at least 0.5, a cation equivalent expressed as a monovalent cation species M + /Al of 0.9 ⁇ 0.1.
  • the zeolites denominated LZ-220 are the more siliceous forms of the prior known mineral erionite and its synthetic analog, zeolite T, and are prepared therefrom using the present process for silicon substitution.
  • LZ-220 has, in the dehydrated state a chemical composition expressed in terms of mole ratios of oxides: wherein M is a cation having the valence "n" and "x" has a value of at least 8, and preferably in the range of 8 to 20, and having the characteristic crystal structure of erionite as indicated by an X-ray powder diffraction pattern having at least the d-spacings set forth in Table K, below, and having extraneous silicon atoms in its crystal lattice in the form of Si0 4 tetrahedra, preferably in an amount of at least 1.0 per 10- 8 ⁇ m 3 (10,000 A3).
  • a more limited subclass of LZ-220 compositions i.e. those which are characterized by having both high molar Si0 2 /A1 2 0 3 ratios and low Defect Structure Factors, can be defined as having a chemical composition expressed in terms of mole fraction of framework tetrahedra as: wherein the mole fraction of aluminum, N, removed from the starting zeolite erionite, is at least 0.3a; the Si/Al has a value 4.0 and preferably greater than 5.0; an increase in the Defect Structure Factor, Az, of less than 0.08, an increase of silicon in the framework of at least 0.5, a cation equivalent expressed as a monovalent cation species M + /Al of 0.9 ⁇ 0.1.
  • the zeolites denominated LZ-213 are the more siliceous forms of the prior known zeolite Omega and are prepared therefrom using the present process for silicon substitution.
  • LZ-213 has, in the dehydrated state, a chemical composition expressed in terms of mole ratios of oxides wherein M is a cation having a valence "n" and "x" is a value greater than 20, preferably in the range of 22 to 60, and the characteristics crystal structural of zeolite Omega as indicated by an X-ray powder diffraction pattern having at least the d-spacings set forth in Table L, below, and having extraneous silicon atoms in its crystal lattice in the form of Si0 4 tetrahedra, preferably in an amount of at least 1.0 per 10- 8 ⁇ m 3 (10,000 A3).
  • a more limited subclass of LZ-213 compositions i.e. those which are characterized by having both high molar Si0 2 /A1 2 0 3 ratios and low Defect Structure Factors, can be defined as having a chemical composition expressed in terms of mole fractions of framework tetrahedra as: wherein the mole fraction of aluminum, N, removed from the starting zeolite Omega is at least 0.3a; the Si/Al has a value 10, and preferably in the range of 11 to 30; an increase in the Defect Structure Factor, Az, of less than 0.08, an increase of silicon in the framework, of at least 0.5; a cation equivalent expressed as a monovalent cation species M + /Al of 0.9 ⁇ 0.1.
  • the cation equivalent of every composition prepared by the method according to the invention is at least 0.8, and more preferably at least 0.85.
  • the cation equivalent values specified for each species subclass is also the preferred value for the other members of the more broadly defined members of each particular species.
  • the framework composition of the LZ-210 product of part (b) of this Example can be expressed:
  • the framework composition of the starting NH 4 Y, used to prepare the LZ-210 product can be expressed: Comparing the LZ-210 product with the NH 4 Y starting material, the change in Defect Structure Factor, Az, is 0.037, well below the preferred maximum specification for LZ-210 of 0.05.
  • the mole fraction of aluminum removed from the framework, N is 0.125, which is substantially greater than the minimum specification that N 0.3a.
  • the increased silicon content of the framework of the LZ-210 product, expressed as a function of the removed aluminum actually replaced by silicon is:
  • the product was 106 percent crystalline.
  • the unit cell (a o ) was 24.49 ⁇ 10 -4 ⁇ m.
  • the DTAexotherm denoting crystal collapse was found at 1037°C.
  • the intensity of the infrared OH absorption band measured at 3710 cm- 1 following activation of the zeolite wafer at 200°C attributable to (OH) 4 groups in aluminum depleted sites was very small, indicating that very few defect sites were present in the product.
  • the oxygen adsorption capacity of the product measured at -183°C and 0.13 bar (100 Torr) was 25.8 weight percent.
  • the fluorosilicate solution was added to the buffered zeolite slurry at the rate of 117 ml (0.031 gallons) per minute. About 3 hours was required to complete the addition. At the end of the addition period, the resultant mixture was heated to 95°C with continuous agitation for a period of 16 hours, filtered, and washed with about 948 I (250 gallons) of water at a temperature of 50°C and dried.
  • the product had the following properties:
  • the framework composition of the starting NH 4 Y expressed in terms of its molar fractions of tetrahedra can be stated thusly:
  • the Defect Structure Factor, z, for the LZ-210 product is 0.055; the infrared absolute absorbance measured at 3710 cm- 1 was 0.130.
  • the framework composition of the LZ-210 product can be expressed as:
  • the change in the Defect Structure Factor, Az, for the LZ-210 is 0.055.
  • the mole fraction of aluminum removed, N, is 0.151 and the amount of removed aluminum replaced by silicon is All other characteristic properties of the modified zeolite compositions of this invention, i.e. X-ray powder diffraction pattern and infrared spectra were exhibited by the product of this example.
  • the framework mole fractions of tetrahedra are set forth below for the starting NH 4 Y and the LZ-210 product.
  • the analytical data show conclusively that framework aluminum was removed and replaced by silicon as a result of the fluorosilicate treatment.
  • the X-ray crystallinity was fully maintained and the unit cell dimension decreased as would be expected due to the smaller atomic size of silicon with respect to aluminum.
  • One hundred grams of an ammonium-exchanged zeolite X having a molar Si0 2 /A1 2 0 3 ratio of 2.52 was slurried in 1000 ml of an aqueous 2.0 molar solution of ammonium acetate at a temperature of 75°C.
  • Five hundred milliliters of a second aqueous solution containing 59.75 grams of ammonium fluorosilicate was added to the slurry in 10 ml increments at a rate of 10 ml every 5 minutes.
  • the stoichiometric ratio of moles of silicon added to the moles of aluminum present in the zeolite was 0.50.
  • zeolite N-A prepared hydrothermally using a combination of sodium hydroxide and tetramethylammonium hydroxide in accordance with the teachings of US-Patent 3,305,922
  • Si0 2 /A1 2 0 3 molar ratio of 6.0 was calcined in air at 550°C for 17 hours to remove the tetramethylammonium cations.
  • the resulting decationized form of the zeolite was ion-exchanged with an aqueous solution of NH 4 CI.
  • a twelve gram (anhyd.) sample of the resulting NH 4 -A zeolite was slurried in 300 ml of an aqueous 3.4 molar ammonium acetate solution at 75°C and 100 ml of an aqueous solution containing 4.63 g ammonium fluorosilicate was added thereto in 1 ml increments at the rate of 1 ml per minute.
  • the slurry was digested for 16 hours at 75°C filtered, and the solids then thoroughly washed with water.
  • the framework mole fractions of tetrahedra are set fort h below for t he starting NH 4 -NA and the LZ-215 product.
  • the process of this invention does not create any substantial amount of new defects in the structure is substantiated by the fact that the Defect Structure Factor, "z", increased by only 0.026 as a result of the treatment.
  • the framework infrared spectra show shifts to higher wave numbers following fluorosilicate treatment.
  • the shift of both the asymmetric stretch band and the symmetric stretch band is characteristic of dealumination accompanied by silicon substitution in the framework.
  • In the hydroxyl region of the infrared spectrum of the fluorosilicate treated zeolite there was no increase in the 3745 cm- 1 band due to occluded amorphous SiOH.
  • the Defect Structure Factor of the starting H-Zeolon is quite large. As a result of the treatment it would appear that a substantial number of the original defect sites have been eliminated.
  • the framework mole fractions are set forth below for the starting H-Zeolon and the LZ-211 product.
  • the mole fractions of framework tetrahedra (TO 2 ) are set forth below in Table 6C for the starting H +- mordenite and the LZ-211 product.
  • the infrared spectrum of the hydroxyl region of the fluorosilicate treated sample did not show any increased absorbance at 3745 cm- 1 due to SiOH species.
  • the increase in absorbance at 3710 cm- 1 due to hydrogen bonded OH groups in vacant sites did not increase commensurate with amount of aluminum removed during the treatment.
  • proof of silicon substitution rests primarily on chemical analysis and absolute absorbance measurements in the hydroxyl stretching region of the infrared spectrum (3710 cm- 1 ).
  • the X-ray crystallinity was maintained.
  • the peak area measurement shows the same value as the starting H + -mordenite and the peak intensity measurement indicates an increase in intensity due to peak sharpening. This suggests a more ordered structure than the starting H + -mordenite, the exact nature of which is not known at this time.
  • the calculated unit cell values make it quite certain that a substantial amount of silicon has replaced aluminum in the framework. This alone could be the cause of increased intensity measurements in the X-ray powder pattern.
  • a sample taken after 24 hours of the fluorosilicate treatment had a Si0 2 /A1 2 0 3 ratio of 19:1, a fluoride content of 3.5 wt.% and absolute absorbance at 3710 cm- 1 of 0.330.
  • the framework mole fractions are set forth in Table 8C below for the starting NH 4 L and the LZ-212 product.
  • the framework mole fractions are set forth below in Table 9C for the starting NH 4 L and the LZ-212 product.
  • fluorosilicate digestion temperature in the present example was 75°C while that in the previous example was at reflux.
  • the degree of dealumination is the same for both digestion temperatures while the efficiency of silicon substitution is substantially reduced at the lower digestion temperature.
  • the framework mole fractions are set forth in Table 10C below for the starting NH 4 -clinoptilolite and the product.
  • the framework mole fractions are set forth in Table 11C below for the starting NH 4 chabazite and the LZ-218 products
  • the framework mole fractions are set forth in Table 12C below fort he starting NH 4 -erionite and the product zeolite.
  • the framework mole fractions are set forth in Table 13C below for the starting NH 4 offretite and the LZ-217 product.
  • the framework mole fractions are set forth in Table 14C below for the starting NH 4 W and the product zeolite.
  • the data establishes the feasibility of substituting silicon for framework aluminum in zeolite W using the process of the present invention.
  • the X-ray crystallinity data coupled with some preliminary adsorption data indicate that an undue amount of crystal degradation occurred using the specified reaction conditions, with the consequent production of a zeolite which does not qualify as preferred LZ-216.
  • Evidence for silicon substitution is established by the shift of framework infrared absorption bands to higher wavenumbers and the relative size of the broad absorption band in the hydroxyl region of the infrared spectrum which does not correlate well with the high level of dealumination. Chemical anlaysis data of both the solid and the liquid phases of the reaction showed that silicon was indeed incorporated into the zeolite. With no increased absorbance at 3745 cm- 1 of the infrared spectrum indicative of amorphous SiOH species as additional evidence, it must be concluded that silicon was incorporated into the zeolite framework during the treatment.
  • LZ-216 The cause of the structure degradation is believed to be the extensive dealumination of the framework without adequate silicon substitution. Accordingly the reaction should, in order to produce LZ-216, be carried out in the presence of a buffer solution such as ammonium acetate. As a general proposition the higher the aluminum content of the starting zeolite, the greater the need for buffering. When this is done, preferred LZ-216 results as the product.
  • a buffer solution such as ammonium acetate
  • NH 4 Rho zeolite which contained a sparingly soluble chloride salt was extracted for a period of eight days in a Soxhlet extraction apparatus. From the washed NH 4 Rho zeolite 25.0 g (anhydrous weight) was slurried in 200 ml distilled water heated at 75°C. A second solution of 100 ml containing 8.5 g (NH 4 ) 2 SiF 6 was added to the slurry in 3 ml increments at a rate of 3 ml every five minutes. During the course of the fluorosilicate addition the slurry temperature was maintained at 75°C.
  • the framework tetrahedral mole fractions are set forth in Table 15C below for both the starting NH 4 Rho and the product zeolite.
  • a LZ-214 product having the characteristic crystal structure of zeolite Rho is produced by digesting at a higher temperature and employing additional buffering agents to protect the zeolite from acid attack.
  • the framework mole fractions of tetrahedra are set forth below for the starting NH 4 and the LZ-210 product.
  • the crystal collapse temperature of the LZ-210 product as measured by the standard DTA procedure was at 1128°C.
  • the untreated NH 4 Y crystal collapse temperature measured by the same DTA technique was at 890°C.
  • the framework mole fractions of tetrahedra are set forth below for the starting NH 4 Y and the LZ-210 product.
  • the crystal collapse temperature of the LZ-210 product as measured by the standard DTA procedure was at 1072°C.
  • the untreated NH 4 Y crystal collapse temperature measured by the same DTA technique was at 890°C.
  • the X-ray powder pattern obtained on the product showed the presence of a substantial amount of (NH 4 )MgAlF 6 in the product.
  • the fluoride containing product was Soxhlet extracted with waterfor 60 hours with the result that a negligible amount of NH 4 MgAlF 6 was removed from the product.
  • the chemical and other analyses for the starting NH 4 Y zeolite and the LZ-210 product zeolite are set forth below:
  • the framework mole fractions tetrahedra are set forth below for the starting NH 4 Y and the LZ-210 product which has been corrected for the presence of 15 wt.% NH 4 MgAIF s .
  • the stoichiometric ratio of moles of Si added as [(NH 4 ) 2 SiF 6 ] to the moles of Al present in the zeolite was 0.55.
  • the slurry was digested 3 hours at 95°C, then filtered and thoroughly washed until tests of the wash water proved negative for both aluminum and fluoride ions.
  • the framework mole fractions are set forth below for the starting NH 4 + -omega and the LZ-213 product.
  • This example is illustrative of a zeolite sample that has been both treated too harshly (high temperature and pH, concentrations) causing excessive crystal degradation, and too mildly such that the dealumination was too slow and silicon substitution could not occur to a substantial level even though the efficiency of silicon substitution was nearly 40%.
  • the zeolite compositions* of the present invention are useful in all adsorption, ion-exchange and catalytic processes in which their less siliceous precursors have heretofore been suitably employed.
  • they are more highly siliceous than their precursors they are not only more thermally and hydrothermally stable than those prior known materials but also have increased resistance toward acidic agents such as mineral and organic acids, SO 2 , S0 3 , NO X and the like.
  • These new zeolites are thus highly useful as selective adsorbents for these materials from, for example, gas streams containing same in contact sulfuric acid plants.
  • these zeolite compositions are readily tailored by known methods to suit the requirements of a broad spectrum of catalyst compositions, particularly hydrocarbon conversion catalysts.
  • the non-metallic cation sites can also be thermally decationized in the known manner to produce the highly acidic zeolite forms favored in most hydrocarbon conversion reactions.
  • the zeolites * of this invention can be compounded into a porous inorganic matrix such as silica-alumina, silica-magnesia, silica-zirconia, silica-alumina-thoria, silica-alumina-magnesia and the like.
  • a porous inorganic matrix such as silica-alumina, silica-magnesia, silica-zirconia, silica-alumina-thoria, silica-alumina-magnesia and the like.
  • the relative proportions of finely divided zeolite and inorganic matrix can vary widely with the zeolite content ranging from about 1 to 90 percent by weight, preferably from about 2 to about 50 percent by weight. * obtained by the method
  • hydrocarbon conversion reactions catalyzed by these new compositions are cracking, hydrocracking, alkylation of both the aromatic and isoparaffin types, isomerization including xylene isomerization, polymerization, reforming, hydrogenation, dehydrogenation, transalkylation and dealkylation, and catalytic dewaxing.
  • zeolite catalyst compositions which contain a hydrogenation promoter such as platinum or palladium, heavy petroleum residual stocks, cyclic stocks and other hydrocrackable charge stocks can be hydrocracked at temperatures in the range of 204°C to 440°C using molar ratios of hydrogen to hydrocarbon in the range of between 2 and 80 gauge, pressures between 0.7 and 241 bar, and a liquid hourly space velocity (LHSV) of from 0.1 to 20, preferably 1.0 to 10.
  • a hydrogenation promoter such as platinum or palladium
  • heavy petroleum residual stocks, cyclic stocks and other hydrocrackable charge stocks can be hydrocracked at temperatures in the range of 204°C to 440°C using molar ratios of hydrogen to hydrocarbon in the range of between 2 and 80 gauge, pressures between 0.7 and 241 bar, and a liquid hourly space velocity (LHSV) of from 0.1 to 20, preferably 1.0 to 10.
  • LHSV liquid hourly space velocity
  • the catalyst compositions employed in hydrocracking are also suitable for use in reforming processes in which the hydrocarbon feedstocks contact the catalyst at temperatures of from about 371 °C to 538°C, hydrogen gauge pressures of from 6.9 to 34.5 bar, LHSV values in the range of 0.1 to 10 and hydrogen to hydrocarbon molar ratios in the range of 1 to 20, preferably between 4 and 12.
  • Hydroisomerization is carried out at a temperature of from about 93°C to 316°C, preferably 149°C to 288°C with an LHSV value of from about 0.2 to 1.0. Hydrogen is supplied to the reactor in admixture with the hydrocarbon feedstock in molar proportions (H/Hc) of between 1 and 5.
  • the same catalyst compositions are used to hydroisomerize normal paraffins.
  • the paraffn feedstock comprises normal paraffins having a carbon number range of C 7 -C 20 -
  • Contact time between the feedstock and the catalyst is generally relatively short to avoid undesirable side reactions such as olefin polymerization and paraffin cracking.
  • LHSV values in the range of 0.1 to 10, preferably 1.0 to 6.0 are suitable.
  • the increase in the molar Si0 2 /AI 2 0 3 ratios of the present zeolite compositions favor their use as catalysts in the conversion of alkylaromatic compounds, particularly the catalytic disproportionation of toluene, ethylene, trimethyl benzenes, tetramethylbenzenes and the like. In the disproportionation process isomerization and transalkylation can also occur.
  • the catalyst form employed contains less than 1.0 weight percent sodium as Na 2 0 and is principally in the so-called hydrogen cation or decationized form.
  • Group VIII noble metal adjuvents alone or in conjunction with Group VI-B metals such as tungsten, molybdenum and chromium are preferably included in the catalyst composition in amounts of from about 3 to 15 weight % of the overall composition.
  • Extraneous hydrogen can, but need not be present in the reaction zone which is maintained at a temperature of from about 204°C to 700°C, gauge pressures in the range of 6.9 to 138 bar and LHSV values in the range of 0.1 to 15.
  • Catalytic cracking processes are preferably carried out using those zeolites * of this invention which have Si0 2 /A1 2 0 3 molar ratios of 8 to 12, less than 1.0 weight % Na 2 0 and feedstocks such as gas oils, heavy naphthas, deasphalted crude oil residua etc. with gasoline being the principal desired product.
  • feedstocks such as gas oils, heavy naphthas, deasphalted crude oil residua etc.
  • gasoline being the principal desired product.
  • the decationized form of the zeolite and/or polyvalent metal cationic form are advantageously employed.
  • Temperature conditions of 454°C to 533°C, LHSV values of 0.5 to 10 and gauge pressure conditions of from about 0 to 3.5 bar are suitable.
  • Dehydrocyclization reactions employing paraffinic hydrocarbon feedstocks, preferably normal paraffins having more than 6 carbon atoms, to form benzene, xylenes, toluene and the like are carried out using essentially the same reaction conditions as for catalytic cracking.
  • the preferred form of the zeolite employed as the catalyst is that in which the cations are principally metals of Group II-A and/or II-B such as calcium, strontium, magnesium.
  • Group VIII non-noble metal cation can also be employed such as cobalt and nickel.
  • the primary objective is to promote the selective hydrodecomposition of organic sulfur and/or nitrogen compounds in the feed, without substantially affecting hydrocarbon molecules therein.
  • Feedstocks include gasoline fractions, kerosenes, jet fuel fractions, diesel fractions, light and heavy gas oils, deasphalted crude oil residua and the like any of which may contain up to about 5 weight percent of sulfur and up to about 3 weight percent of nitrogen.
  • Isomerization reactions are carried out under conditions similar to those described above for reforming, using somewhat more acidic catalysts.
  • Olefins are preferably isomerized at temperatures of 260°C-482°C, while paraffins, naphthenes and alkyl aromatics are isomerized at temperatures of 371°C-538°C.
  • Particularly desirable isomerization reactions contemplated herein include the conversion of n-heptane and/or n-octane to isoheptanes, iso-octanes, butane to iso-butane, methylcyclopentane to cyclohexane, meta-xylene and/or ortho-xylene to paraxylene, 1-butene to 2-butene and/or isobutene, n-hexene to isohexene, cyclohexene to methyl-cyclopentene etc.
  • the preferred cation form of the zeolite catalyst is that in which the ion-exchange capacity is about 50-60 percent occupied by polyvalent metals such as Group II-A, Group II-B and rare earth metals, and 5 to 30 percent of the cation sites are either decationized or occupied by hydrogen cations.
  • the polyvalent metal cation form of the zeolite catalyst is preferred with less than 10 equivalent percent of the cations being alkali metal.
  • the temperature is usually at least 177°C and ranges up to a temperature at which substantial cracking of the feedstock or conversion products occurs, generally up to about 371 °C.
  • the temperature is preferably at least 232°C and not greater than the critical temperature of the compound undergoing dealkylation.
  • Pressure conditions are applied to retain at least the aromatic feed in the liquid state.
  • the temperature can be as low as 121°C but is preferably at least 177°C.
  • the preferred alkylating agents are olefins such as ethylene and propylene.
  • the hydrothermal stability of many of the zeolite compositions* of this invention can be enhanced by conventional steaming procedures.
  • the ammonium or hydrogen cation forms of the zeolite are contacted with steam at a water vapor pressure of at least about 0.1 psia, preferably at least 0.2 psia up to several atmospheres.
  • steam at one atmosphere is employed.
  • the steaming temperatures range from 100°C up to the crystal destruction temperature of the zeolite, but are preferably in the range of 600°C to 850°C. Steaming periods of a few minutes, e.g. 10 minutes, up to several hours can be employed depending upon the specific temperature conditions.
  • the steaming also produces changes in the selectivity of the catalyst in many cases.
  • the preferred zeolite catalysts are those in which the zeolite constituent has pores of sufficient diameter to adsorb benzene.
  • Such zeolites include LZ-210, LZ-211, LZ-212, LZ-217 and LZ-213.
  • the powdered LZ-210 was admixed with 1.5 times its weight of alumina and formed by means of extrusion into 1/16" pellets. The pellets were calcined at 500°C for 6 hours. The resulting extrudates were sized to 60-100 mesh and evaluated for cracking activity using a gas oil feedstock, (Amoco FHC-893), in accordance with the procedure of ASTM test No. D 032,04. The following results were obtained:
  • H 2 /oil 8000 SCF/BBL.
  • the feed was doped with 5000 ppm sulfur as throphene.
  • the activity in this regard was, in terms of the temperature required to obtain a 49.0 °API product after 100 hours in stream, 259°C. to determine the first stage (cracking) activity, the feed was doped with 5000 ppm sulfur as thiophene and 2000 ppm nitrogen as 5-butylamine.
  • the activity in this regard in terms of the temperature required to obtain a 47.0 °API product after 100 hours on stream, was 367°C.

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Claims (29)

1. Verfahren zum Einbau von Siliciumatomen als Si04-Tetraeder in das Kristallgitter eines Aluminosilikatzeolithen, das das In-Kontakt-Bringen eines kristallinen zeolithischen Alumosilikats mit einem molaren Si02/A1203-Verhältnis von mindestens 3 und Porendurchmessern von mindestens 3.10-4 f..lm mit einem Fluorosilikatsalz in einer Menge von mindestens 0,0075 Mol/100 g des zeolithischen Alumosilikats auf wasserfreier Basis umfasst, wobei das Fluorosilikatsalz in Form einer wässrigen Lösung mit einem pH-Wert im Bereich von 3 bis 7 vorliegt und mit dem zeolithischen Alumosilikat mit einer hinreichend langsamen Geschwindigkeit in Kontakt gebracht wird, um wenigstens 60% der Kristallinität der zeolithischen Alumosilikat-Ausgangsverbindung zu erhalten.
2. Verfahren nach Anspruch 1, bei dem die kristalline zeolithische Alumosilikat-Ausgangsverbindung wenigstens teilweise in der Ammoniumkation-Form vorliegt.
3. Verfahren nach Anspruch 2, bei dem das Fluorosilikatsalz Ammoniumfluorosilikat ist.
4. Verfahren nach Anspruch 2, bei dem die zeolithische Alumosilikat-Ausgangsverbindung im wesentlichen die Kristallstruktur von Zeolith Y besitzt.
5. Verfahren nach Anspruch 2, bei dem die zeolithische Alumosilikat-Ausgangsverbindung im wesentlichen die Kristallstruktur von Mordenit besitzt.
6. Verfahren nach Anspruch 2, bei dem die zeolithische Alumosilikat-Ausgangsverbindung im wesentlichen die Kristallstruktur von Zeolith Omega besitzt.
7. Verfahren nach Anspruch 2, bei dem die zeolithische Alumosilikat-Ausgangsverbindung im wesentlichen die Kristallstruktur von Zeolith Rho besitzt.
8. Verfahren nach Anspruch 2, bei dem die zeolithische Alumosilikat-Ausgangsverbindung im wesentlichen die Kristallstruktur von Zeolith L besitzt.
9. Verfahren nach Anspruch 2, bei dem die zeolithische Alumosilikat-Ausgangsverbindung im wesentlichen die Kristallstruktur von Zeolith W besitzt.
10. Verfahren nach Anspruch 2, bei dem die zeolithische Alumosilikat-Ausgangsverbindung im wesentlichen die Kristallstruktur von Zeolith N-A besitzt.
11. Verfahren nach Anspruch 2, bei dem die zeolithische Alumosilikat-Ausgangsverbindung im wesentlichen die Kristallstruktur von Offretit besitzt.
12. Verfahren nach Anspruch 2, bei dem die zeolithische Alumosilikat-Ausgangsverbindung im wesentlichen die Kristallstruktur von Clinoptilolit besitzt.
13. Verfahren nach Anspruch 2, bei dem die zeolithische Alumosilikat-Ausgangsverbindung im wesentlichen die Kristallstruktur von Chabazit besitzt.
14. Verfahren nach Anspruch 2, bei dem die zeolithische Alumosilikat-Ausgangsverbindung im wesentlichen die Kristallstruktur von Erionit besitzt.
15. Verfahren nach Anspruch 1, bei dem die zeolithische Alumosilikat-Ausgangsverbindung Zeolith Y mit einem molaren Si02:AI203-Verhältnis von 3 bis 7 ist, die Reaktion bei einer Temperatur zwischen 20 und 95°C durchgeführt wird und das Fluorosilikatsalz in mindestens der durch die Gleichung
Figure imgb0129
bestimmten Menge eingesetzt wird, wobei AFS die Mindestmolzahl von Fluorosilikatsalz pro 100 g des Zeolith-Ausgangsmaterials auf wasserfreier Basis und "a" die Molfraktion von Gitter-Aluminium-Tetraedern des Ausgangszeoliths Y ist, wie durch die Formel (Alasibmz)02 ausgedrückt ist, in derAl die Gitter-Aluminium-Tetraeder, Si die Gitter-Silicium-Tetraeder und 11 Fehlstellen bedeuten, und "b" die Molfraktion der Siliciumtetraeder und "z" die Molfraktion der Fehlstellen sind.
16. Verwendung eines kristallinen zeolithischen Aluminosilikats, hergestellt mit einem Verfahren nach irgendeinem der Ansprüche 1 bis 15 in einem Verfahren zur Umwandlung von Kohlenwasserstoffen, bei dem ein Kohlenwasserstoff unter Konversionsbedingungen mit dem genannten kristallinen zeolithischen Aluminosilikat in Kontakt gebracht wird.
17. Verwendung eines kristallinen zeolithischen Aluminosilikats in einem Verfahren zur Umwandlung von Kohlenwasserstoffen nach Anspruch 16, wobei der genannte Prozess katalytisches Cracken ist.
18. Verwendung eines kristallinen zeolithischen Aluminosilikats in einem Verfahren zur Umwandlung von Kohlenwasserstoffen nach Anspruch 16, wobei der genannte Prozess Hydrocracken ist.
19. Verwendung eines kristallinen zeolithischen Aluminosilikats in einem Verfahren zur Umwandlung von Kohlenwasserstoffen nach Anspruch 16, wobei der genannte Prozess die Alkylierung ist.
20. Verwendung eines kristallinen zeolithischen Aluminosilikats in einem Verfahren zur Umwandlung von Kohlenwasserstoffen nach Anspruch 16, wobei der genannte Prozess die Isomerisierung ist.
21. Verwendung eines kristallinen zeolithischen Aluminosilikats in einem Verfahren zur Umwandlung von Kohlenwasserstoffen nach Anspruch 16, wobei der genannte Prozess ein Hydrofining-Verfahren ist.
22. Verwendung eines kristallinen zeolithischen Aluminosilikats in einem Verfahren zur Umwandlung von Kohlenwasserstoffen nach Anspruch 16, wobei der genannte Prozess ein Reforming-Prozess ist.
23. Verwendung eines kristallinen zeolithischen Aluminosilikats, hergestellt durch ein Verfahren nach Anspruch 4, in der dekationisierten Form des Zeolithen und/oder kationischen Form mehrwertiger Metalle für ein katalytisches Crack-Verfahren, bei dem ein Kohlenwasserstoff mit dem genannten kristallinen zeolithischen Aluminosilikat unter Crackbedingungen in Berührung gebracht wird.
24. Verwendung eines kristallinen zeolithischen Aluminosilikats, hergestellt durch ein Verfahren nach Anspruch 11, für ein Verfahren zur Umwandlung von Kohlenwasserstoffen, bei dem ein Kohlenwasserstoff mit dem genannten kristallinen zeolithischen Aluminosilikat unter Konversionsbedingungen in Berührung gebracht wird.
25. Verwendung eines kristallinen zeolithischen Aluminosilikats in einem Verfahren zur Umwandlung von Kohlenwasserstoffen nach Anspruch 4, wobei der genannte Prozess das Hydrocracken ist.
26. Verwendung eines kristallinen zeolithischen Aluminosilikats in einem Verfahren zur Umwandlung von Kohlenwasserstoffen nach Anspruch 24, wobei der genannte Prozess das katalytische Cracken ist.
27. Verwendung eines kristallinen zeolithischen Aluminosilikats in einem Verfahren zur Umwandlung von Kohlenwasserstoffen nach Anspruch 24, wobei der genannte Prozess der Alkylierungsprozess ist.
28. Verwendung eines kristallinen zeolithischen Aluminosilikats in einem Verfahren zur Umwandlung von Kohlenwasserstoffen nach Anspruch 24, wobei der genannte Prozess das katalytische Entparaffinieren ist.
29. Verwendung eines kristallinen zeolithischen Aluminosilikats in einem Verfahren zur Umwandlung von Kohlenwasserstoffen nach Anspruch 24, wobei der genannte Prozess die Xylol-Isomerisierung ist.
EP19810110629 1981-10-28 1981-12-20 Mit Silicium substituierte Zeolithzusammensetzungen und Verfahren zu ihrer Herstellung Expired - Lifetime EP0082211B2 (de)

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